JPH0297963A - Electrophotographic sensitive body and image forming method - Google Patents

Abstract

PURPOSE:To improve the electrifiability and the optical sensitivity of the subject body and the stability of the electrifiability and the optical sensitivity against environmental changes of the body by incorporating a specified quinone compd. in a charge generating layer. CONSTITUTION:In the potosensitive body obtd. by laminating the charge generat ing layer 1 and the charge transfer layer 2 on a substrate body 3 in this order, the layer 1 is formed by applying a coating solution dispersed a charge generat ing pigment (A) having positive hole transferring property nd the quinone compd. shown by formula I in a binding resin solution on the substrate body 3. In the formula, A and B are each a group capable of forming a prescribed ring. The compd. shown by the formula is preferably incorporated in the component (A) in an amount of 0.01-2 equivalents on the basis of the component (A), and is composed of a compd. shown by formula (II), etc. The component (A) is preferably composed of a squarylium type pigment (such as a compd. shown by formula III), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrophotographic photoreceptor and an image forming method using the same, and in particular, to an electrophotographic photoreceptor and an image forming method using the same. The present invention relates to an electrophotographic photoreceptor.

Conventional technology Conventionally, electrophotographic photoreceptors include selenium, selenium alloys,
Those using inorganic photoconductive materials such as zinc oxide and cadmium sulfide have mainly been used. However, electrophotographic photoreceptors using inorganic photoconductive materials have limited productivity, cost, and
There were problems with flexibility, etc.

In recent years, in order to solve the shortcomings of inorganic photoconductive materials, research into electrophotographic photoreceptors using organic photoconductive materials has been actively conducted, and electrophotographic photoreceptors made of polyvinylcarbazole and 2,4,7-dolinitrofluorenone have been actively researched. Electrophotographic photoreceptors using a transfer complex and electrophotographic photoreceptors using a eutectic complex of pyrylium salt and alkylidene diarylene are known.

Recently, electrophotographic photoreceptors have been proposed in which the functions of absorbing light and generating electric charges and transporting the generated electric charges are divided into separate materials. Contains h'! A layered type has been proposed. (For example, see JP-A-58-16247.) Furthermore, in recent years, it has been proposed to include a cyanvinyl compound together with an electron donating charge transfer substance in the charge transport layer to prevent an increase in residual potential. There is.

(Japanese Unexamined Patent Publication No. 58-7643 @ Publication) Problems to be Solved by the Invention However, electrophotographic photoreceptors using these organic photoconductive materials have low photosensitivity and are not yet sufficient as photoreceptors. There wasn't. Further, a laminated electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are functionally separated has not yet been sufficiently satisfactory for practical use.

That is, even in the conventionally proposed multilayer electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a support, the photosensitivity is still insufficient, and the photosensitivity and charging potential are insufficient. There were many problems in that the voltage changed significantly with environmental changes and that the potential cycle fluctuations between exposed and non-exposed areas were large.

This kind of problem can also be seen in the normal process of developing the unexposed area on the photoreceptor with 1 to toner and then transferring the toner image to a transfer material such as paper, but especially when the photoreceptor is uniformly This phenomenon is conspicuous in image forming methods that include steps of forming an electrostatic latent image by negatively charging a toner image, forming a toner image by development, and applying a positive charge during transfer. That is, since the potential of the exposed and non-exposed parts of the photoreceptor causes wide cyclical fluctuations, the initial image and the image after copying a large number of sheets are different from each other.
If the density of the transferred image differs significantly, or fog occurs in the transferred image, or if you change the size of the transfer paper to a larger size after copying a large number of copies, the transfer paper under the transfer paper may The disadvantages were that the transfer density was high in the area corresponding to the width difference and fogging occurred.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to solve the above-mentioned problems in the conventional technology.

That is, the object of the present invention is to have good chargeability, high photosensitivity,
The object of the present invention is to provide an electrophotographic photoreceptor whose photosensitivity and charging potential are stable against environmental changes, and whose potentials in exposed and non-exposed areas are stable even when a large number of images are projected.

Another object of the present invention is to uniformly charge a photoreceptor negatively to form an electrostatic latent image, and then apply negatively charged toner to a low potential portion of the electrostatic latent image to form a toner image. Another object of the present invention is to provide an electrophotographic photoreceptor suitable for use in an image forming method that includes a step of performing transfer by applying a charge of a certain polarity.

Still another object of the present invention is to uniformly charge a photoreceptor negatively;
After forming an electrostatic latent image, negatively charged toner is attached to the low potential part of the electrostatic latent image to form a toner image, and the process is transferred by applying a charge of a certain polarity. It is an object of the present invention to provide an electrophotographic image forming method that, when applied to a photographic process, can obtain an image with uniform image density without causing large cyclical fluctuations in the potential of exposed and non-exposed areas.

Means and Effects for Solving the Problems The above-mentioned object of the present invention is to provide an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a support, in which the charge generation layer is formed in a binder resin. This is achieved by using a material containing a pore-transporting charge-generating pigment and a quinone compound represented by the following formula (1).

That is, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a support, in which the charge generation layer has hole transporting charge generation in a binder resin. It is characterized by containing a pigment and a quinone compound represented by the following formula (I).

[wherein A and B represent a ring-forming group selected from the following formulas 1), (2) and <3, respectively, provided that at least one of A and B ) or (■) indicates a group necessary to form a ring.

(1') (2) (3)
(However, X represents a selenium atom or a sulfur atom, R and R
2 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, or an arylcarbonyl group, and R3 represents a hydrogen atom, an alkyl group, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, or an arylcarbonyl group. group, nitro group, cyano group, or benzyloxy group)] The electrophotographic photoreceptor of the present invention will be described below.

1 to 4 are schematic cross-sectional views showing the laminated structure of the electrophotographic photoreceptor of the present invention. In FIG. 1, a charge generation layer 1 and a charge transport layer 2 are sequentially provided on a conductive support 3. In FIG. 2, the conductive support 3
An undercoat layer 4 is provided between the charge generating layer 1 and the charge generating layer 1 . Third
In the figure, a protective layer 5 is provided on the surface of the charge transport layer 3, and in FIG. 4, a subbing layer 4 is provided between the conductive support 3 and the charge generation layer 1, and the charge transport layer A protective layer 5 is provided on the surface of 2.

Next, each layer constituting the electrophotographic photoreceptor of the present invention will be explained.

Conductive supports include aluminum, copper, iron, zinc,
Drums of metal such as nickel, and aluminum, copper, gold, silver, platinum, on sheets, paper, plastic or glass.
Deposit metals such as palladium, titanium, nickel-chromium, stainless steel, copper-indium, conductive metal compounds such as indium oxide and tin oxide, laminate metal foil, or deposit carbon black, oxide, etc. Known materials such as drum-shaped, sheet-shaped, plate-shaped materials can be used, which are conductive-treated by dispersing indium, tin oxide-antimony oxide powder, metal powder, etc. in a binder resin and applying the coating.

Further, if necessary, the surface of the conductive support can be subjected to various treatments as long as the image quality is not affected. for example,
For the purpose of preventing interference fringes that occur when the surface is subjected to oxidation treatment, chemical treatment, coloring treatment, or when coherent light such as laser light is used for image exposure, the surface of the conductive support is coated with
A light absorption layer may be provided or a light scattering treatment may be performed. Light scattering treatment methods include sandblasting, liquid honing, magnetic polishing, buffing ω1, belt sanding, brush polishing, steel wool, acid etching,
Alkaline etching method, electrochemical etching method, etc. can be used.

Further, a subbing layer may be further provided between the conductive support and the charge generation layer. This subbing layer prevents the injection of charge from the conductive support to the photosensitive layer when the photosensitive layer consisting of a laminated structure is charged, and also holds the photosensitive layer adhesively attached to the conductive support. In some cases, the conductive support acts as a contact layer to prevent light from fouling the conductive support.

The binder resin used for this undercoat layer is polyethylene, polypropylene, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate, polyurethane, polyimide resin, nylidene chloride resin, polyvinyl acetal resin. , vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, water-soluble polyester, nitro-t? /Known resins such as reulose, casein, gelatin, etc. can be used.

The thickness of the undercoat layer is suitably 0.01 to 10 .mu.m, preferably 0.05 to 3 .mu.m. Furthermore, the coating methods used when providing an undercoat layer include blade coating method,
Meyer bar coating method, spray coating method, dip coating method, doto coating method, E method
Conventional methods such as knife coating method and curtain coating method can be used.

In the present invention, the charge generating layer forming the photosensitive layer on the conductive support contains a hole transporting charge generating pigment, a quinone compound represented by the above formula (I>), and a binder resin.

The charge-generating pigment used together with the quinone compound must itself have hole-transporting properties.

To determine whether a charge-generating pigment has hole-transporting properties, the pigment is vapor-deposited or dispersed in a resin at a high concentration and applied to a substrate to create a multilayer, which is then positively or negatively charged. It is sufficient to use a determination method that measures optical attenuation. In the present invention, the term "hole-transporting charge-generating pigment" refers to a pigment that exhibits greater optical attenuation when positively charged than when negatively charged in the above determination method.

In the present invention, the hole-transporting charge-generating pigment includes:
Examples include square lium pigments, phthalocyanine pigments, perylene pigments, and the like.

The square aryllium pigment is represented by the following formula:
Fluorine atom, alkyl group, ``R12R13 (where R
12 and R13 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkylcarbonylalkoxy group, or an aryloxy group, and R6 is -
NR14R15 (here, R14 and R15 each represent an alkyl group, an aryl group, or an aralkyl group), R7 to Rlo are a hydrogen atom, an alkyl group, an aryl group, and -CONHR16 (here, RlB is an alkyl group, aryl group or aralkyl group), a halogen atom, an alkoxy group, or an aryloxy group, R11 represents an alkyl group, an aryl group, or an aralkyl group, and Z is 〉CR1□R18, -3--CR1□=CR
18- (wherein R1□ and R18 each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group)] Specifically, for example, the following can be exemplified.

The following margin phthalocyanine pigments are as follows - Defeat (III)
I can list what is shown in .

(In the formula, R19 is a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group, a halogen atom, a cyan group, or a nitro' group, and M is two hydrogen atoms, or Cu, N
i N CO1F e 1M n -Cr -TRu
, Pd, In, Sn, Sb, Zn, Mg, Ga, Ge,
It represents a metal atom selected from As, Si, Pl, Ti, V, U, and Pd, E and F each represent a halogen atom or an oxygen atom, and X and y each represent O or 1. However, when M is a divalent metal atom, both X and y represent O; when M is a trivalent metal atom, X is 1, y is O, and M is a tetravalent metal atom. In the case of atoms, X and y both represent 1, when M is V, E is an oxygen atom, X is 1, y represents O, and when M is V, E and F are oxygen atoms. (X and y both represent 1) Specifically, for example, metal-free phthalocyanine, copper phthalocyanine, vanadyl phthalocyanine, titanyl phthalocyanine, aluminum phthalocyanine, gallium phthalocyanine, indium phthalocyanine, thallium phthalocyanine, silicon phthalocyanine, germanium phthalocyanine, tin. Examples include phthalocyanine, button phthalocyanine, and halides of the above-mentioned phthalocyanines.

In addition, as perylene pigments, for example, the following - Defeated (I)
Examples include compounds represented by V).

0 U (wherein R20 is an optionally substituted alkyl group,
(representing an aryl group or an aralkyl group), specifically, the following can be exemplified.

On the other hand, as specific examples of the quinone compound shown in the above-mentioned -defeat (1), the following can be exemplified.

The quinone compound represented by the above margin (I>) can be synthesized by the method of Kosu (2).An example thereof will be shown below.

Synthesis Example 2,3-diaminonaphthoquinone 5.09 (26.5 mmol), acetic acid/water (
1/1) Put 75mi, 1-7 enyl 1,2 under water cooling
-Propanedione 5.99 (39.8m mol)
Then, a solution of 25 m of acetic acid/water (1/1) was added dropwise (about 10 minutes), and the mixture was stirred for 5 minutes.The yellow precipitate formed was filtered and washed with water. This was dissolved in methylene chloride, purified with a silica gel short column (eluted with methylene chloride), and then recrystallized from methylene chloride methanol to produce 2-methyl-3-phenylnaphthoquinone (Example Compound 11), 6.22y.
(78%) was obtained as a yellow powder. Melting point 235-236
℃. The infrared absorption spectrum is shown in FIG.

Examples of the binder resin for the hole-transporting charge-generating pigment and the quinone compound include polystyrene, silicone resin, polycarbonate resin, acrylic resin, methacrylic resin, polyester, vinyl resin, cellulose, alkyd resin, etc. Any conventionally known material can be used.

In the charge generation layer of the present invention, the quinone compound has a ratio of 0.01 to 2
It is contained in an equivalent amount, preferably in a range of 0.1 to 1 equivalent.

If the amount of injury of the quinone compound is less than 0.01 equivalent, the effect on increasing photosensitivity and reducing environmental fluctuations and repetitive fluctuations in the potential of exposed/non-exposed areas will be reduced, and if it is more than 2 equivalents, In an electrophotographic process in which dark decay increases greatly, charging potential decreases, and toner is formed in non-exposed areas, the background area is likely to be fogged, so the above range is preferable.

Further, the hole transporting charge generating pigment is preferably blended in an amount of 0.1 to 10 parts by weight per 1 part by weight of the binder resin.

Various methods can be employed to incorporate the hole-transporting charge-generating pigment and the quinone compound into the charge-generating layer. For example, it can be contained in the following manner. ■A hole-transporting charge-generating pigment and a quinone compound are added together to a binder resin solvent solution and dispersed. Dispersion methods include ball mill dispersion, attritor dispersion, sand mill dispersion, and ultrasonic dispersion. Any commonly employed method can be used. (2) First, a hole-transporting charge-generating pigment is dispersed in a solvent solution of a binder resin, and a quinone compound is added to the resulting dispersion. (2) A hole-transporting charge-generating pigment is previously treated with a quinone compound solution to be adsorbed, and then dispersed in a binder resin solvent solution. (2) A hole-transporting charge-generating pigment is dispersed in a solvent solution of a binder resin, and a film is formed by coating.The film is then treated with a solution of a quinone compound and impregnated.

Furthermore, during this dispersion, the charge generating pigment particles have an average particle size of 3.
It is effective to have a particle size of less than IIM, preferably less than 0.57 m.

In addition, the solvents used for dispersion include methanol,
Ethanol, n-propertool, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone,
Common organic solvents such as methyl acetate, dioxane, tetrahydrofuran, methylene chloride, and chloroform can be used alone or in combination of two or more.

As the coating method used when providing the charge generation layer, a conventional method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method may be used. Can be done.

The thickness of the charge generation layer is generally set in the range of 0.05 to 5 JIM, preferably 0.1 to 2.0 JIM.

The charge transport layer in the electrophotographic photoreceptor of the present invention is formed by containing a charge transport material in a suitable binder resin. As charge transport materials, oxadiazole derivatives such as 2,5-bis(p-diethylaminophenyl)-1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1-[pyridyl- (2)] Pyrazoline derivatives such as -3-(D-diethylaminostyryl)-5-(1)-diethylaminostyryl) pyrazoline, aromatic tertiary amine compounds such as triphenylamine and dibenzylaniline, N, N' -bis-(3-methylphenyl)-
Aromatic tertiary diamino compounds such as [1,1'-biphenyl]-4,4'-diamine, 3-(4'-dimethylaminophenyl)-5,6-di-(4'-methoxyphenyl) - 1,2,4-triazine derivatives such as 1,2,4-triazine, 4-diethylaminobenzaldehyde-1
, hydrazone derivatives such as 1'-diphenylhydrazone,
Quinazoline derivatives such as 2-phenyl-4-styrylquinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di(p-methoxyphenyl)benzofuran, p-(
α-stilbene derivatives such as 2,2-diphenylvinyl)-N,N-diphenylaniline, [Journal of
Imaging Science J
fImaging 5science) 29: 7~l
0 (1985), N-
Carbazole-derived wood such as ethylcarbazole, poly-
N-Donylcarbazoletilglutamate and its derivatives, as well as known charges such as pyrene, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-hyphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, etc. Transport materials can be used, including but not limited to. or,
These charge transport materials can be used alone or in combination of two or more.

Further, as the binder resin, polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polystyrene resin, polyvinyl acetal resin, styrene-butadiene copolymer, vinylidene chloride- Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, methylene alkyd resin, poly-N
- Known resins such as vinyl carbazole can be used, but are not limited thereto. Further, these binder resins can be used alone or in combination of two or more types.

The blending ratio of the charge transport material and the binder resin is 10:1 to 1.
:5 [i ratio] is preferable. The thickness of the charge transport layer used in the present invention is generally 5 to 50 μm, preferably 10 μm.
It is set in the range of ~30.

As a coating method for forming the charge transport layer, conventional methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, and a curtain coating method can be used.

Furthermore, examples of solvents used when forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenbin; ketones such as acetone and 2-butanone;
Common organic solvents such as halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and ethylene chloride, and cyclic or linear ethers such as tetrabitrofuran and ethyl ether are used alone or in combination of two or more. be able to.

In the electrophotographic photoreceptor of the present invention, a protective layer may be provided on the charge transport layer, if necessary. This protective layer is used to prevent chemical deterioration of the charge transport layer when the photosensitive layer having a laminated structure is charged, and to improve the mechanical strength of the photosensitive layer.

This protective layer is formed by containing a conductive material in a suitable binder resin. Examples of conductive materials include metallocene compounds such as N,N'-dimethylferrocene, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,
Materials such as aromatic amino compounds such as [1'-phenyl]-4,4'-diamine, metal oxides such as antimony oxide, tin oxide, titanium oxide, indium oxide, and tin oxide-antimony oxide can be used. Further, as the binder resin used for this protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, etc. can be used. can.

The thickness of the protective layer is 0.5 to 20 μm, preferably 1 to 10 μm.
m range.

The electrophotographic photoreceptor of the present invention can be used in known electrophotographic image forming methods. In other words, it can be used in an image forming method that includes the steps of uniformly negatively charging the surface of a photoreceptor, performing imagewise exposure to form an electrostatic latent image, and developing it with charged toner particles, and is always stable. You can copy an image with the same image density as (q).

However, the electrophotographic photoreceptor of the present invention is particularly suitable for use in the following image forming method of forming an image using a so-called reverse vision imaging method.

In other words, the surface of the present electrophotographic photoreceptor was uniformly negatively charged)
A toner image is formed by applying imagewise exposure to form an electrostatic latent image, attaching negatively charged toner to the low potential area (exposed area) of the electrostatic latent image, and then It is particularly suitable for an image forming method comprising superimposing a transfer material on an electrophotographic photoreceptor to be held, applying a positive charge from the back side of the transfer material, and transferring a toner image onto the transfer material.

To explain the image forming method to which the electrophotographic photoreceptor of the present invention is applied, a corona discharger such as a corotron, scorotron, guicorotron, or pincorotron, a charging roller, etc. are used as means for uniformly charging the surface of the photoreceptor. can. The initial charging potential is preferably set in the range of -100 to -200V.

Image exposure means include an illumination optical system consisting of an illumination lamp and an imaging optical system, a laser exposure optical system consisting of a laser beam generation source and a laser beam deflector, an LED array, a liquid crystal light valve, a vacuum fluorescent tube array, and an optical fiber array. , an optical waveguide array, or the like can be used, but it is preferable to use a light source that emits light with a wavelength in the spectral sensitivity region of the photoreceptor.

The electrostatic latent image formed by imagewise exposure is developed using a developer to form a toner image. As the developer, a two-component developer consisting of carrier and toner or a one-component developer consisting only of toner can be used. The toner particles may be magnetic toner containing magnetic powder inside, or non-magnetic toner. During development, a developing machine having a developer carrier carrying the developer is used to bring the toner particles close to or in contact with the electrostatic latent image.
Toner particles are selectively deposited depending on the potential of the electrostatic latent image.

In this case, depending on the charging polarity of the toner, the toner either adheres to the low potential area (exposed area) of the electrostatic latent image on the photoconductor (reversal development) or to the high potential area (unexposed area) (positive development). transfer and development), but these can be carried out by selecting the charging polarity of the toner. Since the electrophotographic photoreceptor of the present invention is essentially negatively chargeable, in the case of reverse development, a toner with negative charge polarity is selected, and in the case of forward development, a toner with positive charge polarity is selected. toner is selected.

During development, a bias voltage can be applied between the support of the electrophotographic photoreceptor and the developer carrier. As the bias voltage, a DC voltage or an AC voltage superimposed on a DC voltage can be used. Particularly when performing reversal development, it is necessary to apply a bias voltage equal to or lower than the potential of the non-exposed area.

The toner image formed by development can be transferred to a transfer material by any method. As a transfer means,
In addition to the above-mentioned corona charger, a transfer roll to which a transfer voltage is applied, a pressure roll, etc. can be used, but electric field transfer, which uses a corona discharger to transfer by applying a charge from the back side of the transfer material, is particularly effective. be. For example, negatively charged toner particles formed by reverse development are suitably transferred onto the transfer material by applying positive corona discharge from the back side of the transfer material.

After the transfer is completed, if necessary, the photoreceptor is cleaned of residual toner images (toner images that have not been transferred), and then N is removed by an optional optical static eliminator or coroneau static eliminator,
It is prepared for the next image forming process.

Further, the electrophotographic photoreceptor of the present invention can also be suitably used in a so-called one-pass multicolor image forming method.

For example, after the surface of an electrophotographic photoreceptor is uniformly negatively charged, a first image exposure is performed to form a first electrostatic latent image, and the low potential portion of the first electrostatic latent image is A negatively charged toner is deposited to form a first toner image, followed by a second imagewise exposure to form a second electrostatic latent image, and a high potential of the second electrostatic latent image is applied. A second toner image is formed by attaching a positively charged second toner to the area, and then, after aligning the polarities of the first and second toner images to one polarity, the first and second toner images are formed. The transfer material is superimposed on the electrophotographic photoreceptor that holds the
Suitable for use in an image forming method comprising applying charges of polarity opposite to the polarities of the first and second toner images from the back side of the transfer material and transferring the first and second toner images onto the transfer material. Can be done.

In the one-pass multicolor image forming method described above, the same means as described above can be used as the means for uniformly negatively charging the photoreceptor, the image exposure means, the developing means, and the transfer means.

First, the surface of the photoreceptor is uniformly negatively charged, and then a first image exposure is performed. The first image exposure employs image area exposure in which a portion corresponding to the image area is exposed. The formed first electrostatic latent image is developed using a first developer to form a first toner image, but in this case, a bias voltage lower in potential than the initial charging potential is applied. Using a developer carrier, negatively charged first toner is attached to a low potential area (exposed area) of the first electrostatic latent image to form a first toner image.

Next, a second image exposure is performed, and in the second image exposure, a foreground portion exposure is employed in which a portion corresponding to a non-image portion is exposed. Moreover, the light source used for the second image exposure is
The light intensity is made weaker than that used for the first image exposure, and the exposure is performed so that the potential of the photoreceptor corresponding to the background part is reduced to approximately half of the initial charging potential. is preferred.

Next, the parts that were not exposed in the second image exposure (the second
A positively charged second toner is applied to the image area (in the image exposure). In this case, it is preferable to perform development by carrying the second toner on a developer carrying member to which a bias voltage higher than the potential of the photoreceptor corresponding to the background portion is applied.

Furthermore, since the second development is carried out on the photoreceptor on which the first toner has already been carried, so-called overlapping development, there may be image disturbance of the first toner image or damage caused by the second developing machine carrying the first toner. In order to prevent the toner from being mixed into the toner, it is preferable to use a two-component developer consisting of toner and a negatively chargeable low-density carrier in the second development. Also, the carrier density is 4.0Q/cr
Those below A are preferred.

After forming the first and second toner images on the photoreceptor, these toner images are transferred onto a transfer material.

In this case, since these toners are charged with opposite polarities, it is necessary to align them to one of the polarities. In order to align the polarity, corona discharge can be performed using a pre-transfer charger. Since the electrophotographic photoreceptor of the present invention is negatively charged, it is preferable that the toner has a positive polarity. For pre-transfer charging, it is preferable to use an alternating current voltage on which a positive direct current voltage is superimposed.

Next, a transfer material is superimposed on the toner image on the photoreceptor, and the polarity opposite to that of the toner image is applied from the back side of the transfer material. A potential is applied to transfer the toner image onto the transfer material. In this case, it is preferable to use a negative DC voltage as the transfer potential.

Image formation is performed as described above, and the first toner and second toner can be selected from appropriate colors. For example, if the electrophotographic photoreceptor is drum-shaped, the drum A two-color image can be obtained during one revolution.

EXAMPLES Hereinafter, the electrophotographic photoreceptor of the present invention and an image forming method using the same will be explained with reference to examples.

Example 1 Outer diameter 40. The surface of a mirror-cut aluminum pipe with a length of 319 mm is polished by puff polishing to achieve a surface roughness of R.
Processing was performed so that a=0.17JIII&. Next, in order to form an undercoat layer, a mixed solution having the following composition was prepared.

Polyamide resin (Laccamite 5003 manufactured by Dainippon Ink Chemical) 1 part by weight methanol
5 parts by weight n-butanol 3 parts by weight Water 1 part by weight The above mixture was applied by dip coating and dried at 110° C. for 10 minutes to form a subbing layer with a thickness of 1M1.

A mixture of the following components was then prepared.

X-type metal-free phthalocyanine 1 part by weight quinone compound Based on the pigment (example compound 2>
A mixture of 0.3 equivalent polyvinyl butyral resin (trade name: S-LEC B) 11, manufactured by Hosui Kagaku ■) and 60 parts by weight of cyclohexanone was dispersed for 10 hours using a sand mill using 1Mφ glass beads as a dispersion medium. A dispersion of pigment with an average particle size of 0.05 was prepared. The resulting dispersion was applied onto the undercoat layer by dip coating, and dried by heating at 120°C for 10 minutes to give a film thickness of 0.2.
5. An immediate charge generation layer was formed.

Furthermore, a mixture of the following components was prepared.

N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl)-4,4-diamine 2 parts by weight Polycarbonate resin (bisphenol Z type) 3 parts by weight Monochlorobenzene 20 parts by weight This mixture was coated on the charge generation layer by dip coating and dried at 110° C. for 60 minutes to form a charge transport layer with a thickness of 20 pm.

The electrophotographic photoreceptor thus prepared was negatively charged using a scorotron (grid applied voltage: -300V), and then a semiconductor laser (780nll1
The surface electrometer probe was placed at a position 0.3 seconds after exposure (corresponding to the position 0.6 seconds after charging), and the potential (VH) when not exposed was measured. and the potential at the time of exposure (V L : 30 erg/Cm exposure) were measured. Furthermore, a corotron (wire applied voltage: +5.0 KV) is placed after this probe and positively charged, and then,
Static electricity was removed using a tungsten lamp. In this system, one cycle consisted of negative charging-exposure, positive charging, and removal-exposure, and changes in VH and V[ were measured up to 200 cycles.

This measurement was carried out at 32°C, 85%RH: 20°C, 55%R
(2) The test was carried out under each environment of 10° C. and 15% RH. The results are shown in Table 1. In addition, the above electrophotographic photoreceptor can be used with a laser printer (product name: XP-11, Fuji Xerox ■
After continuously printing 500 sheets of A4 size paper, we printed only B4 size paper, and measured the density difference between the area where the A4 size paper passed and the other areas, and the difference between each. Fog in the background area was evaluated under an environment of 32° C. and 185% RH. The results are shown in Table 2 below.

Note that this laser printer uses negative polarity magnetic component toner as the developer, and has a DC+4.8
The toner image attached to the exposed area was transferred using a KV transfer corotron.

Examples 2 to 7 The amount of the quinone compound (Example Compound 2) was adjusted to 0.005 equivalent (Example 2), 0.01 equivalent (Example 3), and O1111°C Example 4) relative to the pigment, respectively. , 1.0 To 11! (Example 5), 2.0 Tow! (Example 6) or 4.0 equivalent (Example 7), electrophotographic photoreceptors were prepared in exactly the same manner as in Example 1, and evaluated in the same manner. The results are shown in Tables 1 and 2.

Comparative Example 1 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 1, except that no quinone compound was added, and evaluated in the same manner. The results are shown in Tables 1 and 2.

Examples 8 to 11 Except for changing the quinone compound to the compound shown in Table 1,
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 1, and evaluated in the same manner. The results are shown in Tables 1 and 2.

Examples 12 to 17 Electrophotographic photoreceptors were prepared in the same manner as in Example 1, except that the X-type metal-free phthalocyanine and quinone compound in Example 1 were changed to the compounds shown in Table 3, and evaluated in the same manner. I did it. The results are shown in Tables 3 and 4.

Comparative Examples 2-7 Examples 12-1 except that no quinone compound was added
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 7, and evaluated in the same manner. The results are shown in Tables 3 and 4.

Examples 18 to 24 with blank spaces below A mirror-cut aluminum pipe with an outer diameter of 84 sφ and a length of 310 m was used as a substrate, perylene pigment (exemplified compound IV-1> was used as a charge-generating pigment, and quinone compound was used as a quinone compound). Except for using the compounds shown in Table 5,
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 1.

The electrophotographic photoreceptor thus prepared was negatively charged using a scorotron (grid applied voltage knee 300V), and then charged with a halogen lamp (however, 550N
The light is attenuated by exposure using an interference filter with a central wavelength of m, and the position after 0.3 seconds (after charging,
The surface potential resistance probe was placed at a position corresponding to the position after 0.6 seconds), and the potential during non-exposure (VH) and the potential during exposure (V[:30
erg/CII! exposure) was measured. Furthermore, after this probe, a corotron (wire applied voltage: +5.0K
V> was placed and positively charged, and then the charge was removed using a tungsten lamp. In this system, one cycle consisted of negative charging-exposure, positive charging, and removal-exposure, and changes in VH and V[ were measured up to 200 cycles. This measurement is 3
The experiments were carried out under the following environments: 2°C, 85% R)l; 20°C, 551RH; and 10°C, 15% RH. The results are shown in Table 5.

Comparative Example 8 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 18, except that no quinone compound was added, and evaluation was performed in the same manner. The results are shown in Table 5.

Comparative Examples 9 and 10 In Example 18, perylene pigment (exemplified compound IV-
Electrophotographic photoreceptors were prepared in exactly the same manner except that dibromoanthanthrone or a dosuazo pigment represented by the following structural formula was used in place of 1>, and evaluations were conducted in the same manner. The results are shown in Table 5.

Comparative Examples 11 and 12 Electrophotographic photoreceptors were prepared in exactly the same manner as in Comparative Examples 9 and 10, except that no quinone compound was added.
Evaluation was conducted in the same manner. The results are shown in Table 5.

Below are blank spaces Example 25 and Comparative Example 13 Using the electrophotographic photoreceptors prepared in Example 1 and Comparative Example 1, a scorotron (grid applied voltage: -30
0V), and then imagewise exposed to a semiconductor laser (780 nm oscillation) to attenuate the light.
A surface electrometer probe was placed at a position 0.3 seconds after exposure (equivalent to the position 0.6 seconds after charging), and the potential during non-exposure (VH) and the potential during exposure (V L : 20erg/
cn exposure)ll! I decided. Further, a corotron (wire applied voltage: 5.0 KV) was placed after the conoprobe to negatively charge it, and then the static electricity was removed using a tungsten lamp. In this system, negative charge-exposure-negative charge-removal exposure is considered as one cycle, and Vl up to 200 cycles.
Changes in l and VL were measured. This measurement was carried out at 32℃, 8
5%R■: 20℃, 55%R11; and 10℃, 15%
It was conducted under each environment of R11. The results are shown in Table 6.

Example 26 and Comparative Example 14 As a base, the surface of an aluminum pipe with an outer diameter of 84 Mφ and a length of 310 mm and a decorative border cutting process was processed by grindstone polishing so that the surface roughness was Ra = 0.15. .

Next, an electrophotographic photoreceptor was produced in the same manner as in Example 1 or Comparative Example 1.

The electrophotographic photoreceptor produced in this way can be copied.
(FX2700 manufactured by Fuji Xerox ■) Two-color laser printer (Charging - Primary laser exposure - Negatively charging red toner development on exposed areas - Secondary laser exposure - Positively charging black toner development on unexposed areas - DC (consisting of AC pre-transfer charging with a superimposed AC charger, transfer by applying a negative DCIO tron, cleaning, and charge removal), and a mixed pattern of red and black was repeated 500 times on B4 size paper.
A sheet was printed and changes in print density in the red and black areas were observed.

In the electrophotographic photoreceptor of Example 26, clear printing with no background fog was obtained in both the red and black areas, but in the electrophotographic photoreceptor of Comparative Example 14, red toner was applied to the background area as well as the number of continuous sheets. The fog started to increase, the red print started to get thicker, and the black print became thinner.

Effects of the Invention The electrophotographic photoreceptor of the present invention has a charge generating layer containing a hole transporting charge generating pigment in a resin and a quinone compound represented by the formula (I) above. Compared to the case where no quinone compound is added, the sensitivity is improved, the charging property is good, the photosensitivity and charging potential are stable against environmental changes, and the exposed and non-exposed areas are It has an excellent effect that the potential is stable without decreasing even when a large number of copies are made.

The electrophotographic photoreceptor of the present invention is particularly useful when applied to an electrophotographic image forming method that repeats the following operations: negative charge, image exposure, reversal development, positive charge transfer, and charge removal, for example, when used in a laser printer, etc. In that case, the surface potential of the photoreceptor during image exposure is maintained from the initial image forming operation to after the image forming operation is repeated many times, with the decrease in potential accompanying repeated image forming operations. A stable surface potential is maintained at all times without any occurrence of fogging, and therefore images with stable image density can be obtained and the occurrence of fog can be suppressed.

In addition, even if the transfer paper is changed to a wider size one after repeating the image forming operation many times, the transfer density will not increase in the area corresponding to the width difference of the transfer paper, and therefore the background It is possible to produce 1 q of images of uniform density with no fog in the area.

Note that if the charge generation layer does not contain the quinone compound, the potential of the exposed and non-exposed areas gradually decreases with repeated image forming operations, the image density gradually increases, and the background area becomes foggy. occurs. Also, if you change the transfer paper to a wider size after repeating the image forming operation many times, you may notice an increase in image density and fog in the background area of the transfer paper in the area corresponding to the width difference. It will be done.

Furthermore, the electrophotographic photoreceptor of the present invention can also be applied to a so-called one-bath multicolor image forming method.

[Brief explanation of drawings]

1 to 4 are schematic cross-sectional views for explaining the structure of the electrophotographic photoreceptor of the present invention, and FIG. 5 shows a quinone represented by the general formula (I) used in the present invention. It is an infrared absorption spectrum diagram of an example of a compound. DESCRIPTION OF SYMBOLS 1... Charge generation layer, 2... Charge transport layer, 3... Conductive support, 4... Subbing layer, 5... Protective layer. Patent applicant Fuji Xerox Co., Ltd. Agent
Patent Attorney Tsuyoshi HorabeFigure 1Figure 2Figure 3Figure 4Figure 42i5 ζ ゐ

Claims (5)

[Claims] (1) In an electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are sequentially laminated on a support, the charge generation layer contains a hole transportable charge generation pigment in a binder resin and the following general formula ( I
) An electrophotographic photoreceptor comprising a quinone compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, A and B represent groups forming a ring selected from the following formulas (1), (2) and (3), respectively, with the exception that A
At least one of and B represents a group necessary to form a ring of formula (1) or (2). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) (However, X is a selenium atom or sulfur R_1 and R_2 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, or an arylcarbonyl group, and R_3 represents a hydrogen atom, an alkyl group, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, alkoxycarbonyl group, arylcarbonyl group, nitro group, cyano group or benzyloxy group)] (2) Claim 1, characterized in that the quinone compound is contained in an amount of 0.01 to 2 equivalents relative to the hole transporting charge generating pigment.
The electrophotographic photoreceptor described above. (3) The electrophotographic photoreceptor according to claim 1, wherein the hole-transporting charge-generating pigment is a phthalocyanine pigment, a squareryllium pigment, or a perylene pigment. (4) After the surface of the electrophotographic photoreceptor according to claim 1 is uniformly negatively charged, imagewise exposure is performed to form an electrostatic latent image, and the low potential portions of the electrostatic latent image are negatively charged. A toner image is formed by adhering the toner, a transfer material is superimposed on an electrophotographic photoreceptor that holds the toner image, and a positive charge is applied from the back side of the transfer material to transfer the toner image onto the transfer material. An image forming method characterized by: (5) After the surface of the electrophotographic photoreceptor according to claim 1 is uniformly negatively charged, a first image exposure is performed to form a first electrostatic latent image, and the first electrostatic latent image is formed. A first toner image is formed by depositing negatively charged toner on the low potential portions of the image;
A second image exposure is performed to form a second electrostatic latent image, and a positively charged second toner is attached to a high potential portion of the second electrostatic latent image to form a second toner image. After forming and aligning the polarities of the first and second toner images to one polarity, a transfer material is superimposed on the electrophotographic photoreceptor holding the first and second toner images, and the back side of the transfer material is An image forming method characterized in that the first and second toner images are transferred onto a transfer material by applying charges having polarities opposite to those of the first and second toner images.